Phenolic-formaldehyde resin compositions



a i n assess-7 rnntsorrc-ronnrarnnnrnn RESIN coMrosrrroNs "Rohert Steckler, Chagrin Fais, @hio, assignortoGeneral The present invention relates to a plasticized phenolicformaldehyde resin composition having excellent flexibility and resistance to flaking or cracking.

It is known that phenols such as phenol per se, resorcinol, alkyl phenols, i.e. cresols, xylenols, phloroglucinol, etc. react with aldehydes (commonly formaldehyde) or ketones to form a variety of products. The nature of the resinous product depends ,on the choice of the phenolic compound and the aldehyde or ketone and on the conditions of the reaction. Phenolic-formaldehyde resins are of two main types. The resins resemble either the phenol alcohols or the dihydroxydiphenylalkanes in basic structure. If they are prepared with an excess of formaldehyde and an alkaline catalyst they will resemble the phenol alcohols and have methylol side or end groups. The molar ratio of formaldehyde phenolic .compound used may vary in a ratio from 1:1 to 3:1, e.g.:

(H-I on 11 HOCHT- 0112 CHr CH2OH 72:1 to 25 Such resins are often referredto as -resoles. They are capable of being curedby the application of heat and sometimes acids, cure resulting through condensation of the methylol groups. By cooling the resin the reactions may be conveniently stopped, or at least effectively retarded, anywhere between the addition of "the formaldehyde and the final curing process. To resume the reaction, the temperature is raised or an acidic catalyst is added. Since there is no sharp break in these reactions such resins have been termed the one-stage resins.

The majority of the one-stage resins employ formaldehyde as the aldehyde, although certain other aldehydes may be used. Formaldehyde is preferred because'of its high reactivity and freedom from side reactions.

On the other hand, if the phenolic resinis prepared with an acidic catalyst and less than a mole of'formaldehyde per mole of phenolic compound, the resin will resemble a dihydroxydiphenylmethane in structure, ue.g., the chains are phenol ended. The molar ratio -:of form aldehyde to phenolic compound used may vary anywhere from 1:2 to 1:1, e.g.:

0=dihydroxydiphenylmethane The resins, commonly referred to as novolak, are permanently soluble and fusible and will cure upon the addition of formaldehyde (in.the formiofipar-aformaldehyde), orhexamethylenetetramine. As the preparation Thermosetting phenolic-formaldehyderesins have .cer-

tain inherent drawbacks which prevent their full commercial use as coating materials "for 'the'formation 'of rates Patent .C. in 1% seconds.

a 45-60% solution, preferably a 50% solution. case, ethanol was employed as the solvent to yield a films. In other words, such resins are brittle and have extremely poor resistance to flaking or cracking. These drawbacks are attributable to the lack of flexibility, elongation and adhesion-of the cured film resulting from such phenolic formaldehyde resins. Attempts to overcome these defects by incorporating any of the commercially available plasticizers yielded no improved results. Dioctyl phthalate, which is one of the most versatile plasticizers for various types of resins, proved ineflective in imparting flexibility and resistance to flaking or cracking of phenolic=formaldehyde resins.

It is an object of'this invention to overcome the foregoing difficulties and to provide-a plasticized phenolicformaldehyde resin which possesses excellent flexibility and elongation, and resistance to flaking or cracking.

Other objects and advantages will become more clearly apparent from the following specification.

I have found that phenolic-formaldehyde resins of the foregoing type, -i.e. prepared from any phenolic compound such as phenol, alkylated phenols, e.g. mand p-cresols, resorcinol, phloroglucinol, xylenol, etc., and formaldehyde, are successfully plasticized by employing a mixture of 30-100 partsby weight of a polyalkoxy acetal and 1-15 parts by weight'of an organic titanium chelate per parts'by Weight, based on the non-volatile content, of a phenoliceformaldehyde resin. It is to be noted that such resins are prepared in solution form, i.e., in volatile solvents such as the'lower alcohols, ketones, etc. Films cast from .such a mixture containing the polyalkoxy acetal and chelate and whether further diluted or not by solvents such as ketones, alcohols, dioxane, etc., display excellent flexibility and resistance to flaking or cracking. The polyalkoxy acetal and the organic titanium chelate is merely blended in the aforestated ratios with the phenolic-formaldehyde resin and the, re-

sulting'co-mposition employed in the preparation of coatings, films, etc.,.in the well known manner.

Since the phenolic-formaldehyde resins are readily available on the openmarket and the procedure for their preparation is well known to those skilled in the art, references to literature or .patents need .not be made herein. However, for purposes of illustration, a procedure which yields aphenolic-forrnaldehyde resin soluble in the lower alcohols, such as methanol, ethanol, npropanol or isopropanol, or ketones, glycol ethers, dioxane, and similar polar solvents, is as follows:

To a 3-necked resinflask, .equipped with a stirrer, thermometer and reflux condenser, were added 927 .parts by weight of phenol, 9.27 parts by weight of formaldehyde (40% aqueous solution) and 10.parts by weight of concentrated ammonia. The mixture was refluxed with agitation until a drop of the reaction mixture cures into a resinous mass on a hot plate at a temperature of 200 When this stage is reached, the resin is then dehydrated at 50 C. and 26" vacuum for a period of 3% hours during which the temperature is finally raised to 100 C. The'resin isthen dissolved in a lower alcohol such as methanol, ethanol, isopropanol to yield In this The resulting phenolic-formaldehyde 50% solution.

resin in solution is of the phenol-alcohol type.

wwhereinR represents an-alk-ylradical'of l to 5 carbon atoms, e.g. methyl, ethyl, propyL'isopropyl, butyl, amyl,

etc., andmuepresents-an integerof 5 to 25.

As illustrations of such polyalkoxy acetals, the following may be mentioned:

The titanium ortho esters utilized in the preparation of the corresponding chelates are well known and are characterized by the following general formula:

A. 1,1,3,5,7-pentamethoxy octane B. 1,1,3,5,7,9-hexamethoxy decane 5 )4 C. 1,1,3,5,7,9,1l-heptamethoxy dodecane wherein R represents an al-kyl group of one of the 3 to 18 D. 1,l,3,5,7,9,11,13-octamethoxy tetradecane carbon atoms, i.e. propyl, butyl, hexyl, octyl, nonyl, E. 1,l-diethoxy-3,5,7-ethoxy decane decyl, dodecyl, cetyl, octadecyl, etc. As illustrations of F. 1,1-dimethoxy-3,5,7-triethoxy octane such titanium ortho esters, many of which are commerlly available I have found the followin to be espe- The 01 alkox acetals are obtained b condensin 1 i g mole of either methanol, ethanol, propa hol, butanol or many adaptable for the Preparatlon 0f the corresponding pentanol with 5-25 moles of vinyl methyl ether. chelates Tetraiso I 1 tita ate The following polyalkoxy acetals were prepared while Tetr 5 3 mania employing 1 mole of a lower alcohol of 1 to 5 carbon atoms with 5 to 25 moles of vinyl methyl ether. For 15 Tetrahex i purposes of simplification and identification, the abbrevia- Tetrwzgtlh llhex 1 titanate tion PMAC followed by a numeral will designate that the Tetrahe t titansgte condensation product was obtained by condensing 1 mole Tetraocf ilfitanate of methanol with the numerical designation in moles of Tetranogl ,itanate vinyl methyl ether. For example, when 1 mole of meth- Tetradecyl tiltanate anol is condensed with 15 moles of vinyl methyl ether, Tetrahenzllec 1 titanate the product is designated as PMAC15; with ethanol it Tetradodec i/fitanate will be designated as PEAC; with propanol PPAC, with Tetracet l tsiltanate butanol PBAC and with pentanol or normal amyl alcohol T y l as PAAC. etrasteary titanate The organic titanium chelates (all of which are com- I' PMAC 15 mercially available under various brand or trade names) I PMAC 25 are, as pointed out above, readily obtained by reacting PEAC 10 in the conventional manner 2, 2.2, 3 or 4 moles of the L PEAC 15 chelating compound such as octylene glycol, triethanolamine, a fatty acid salt of triethanolamine or a fatty acid PBAC 15 of 3 to 18 carbon atoms with 1 mole of any one of the PBAC 25 above titanium ortho esters. The triethanolamine titanate PAAC 10 N-salts of fatty acids are readily obtained by reacting 2 Q. PAAC 15 moles of triethanolamine with 1 mole of the titanium P A AC 20 ester of 1 or 2 moles of a fatty acid. All of the chelates S PAAC 25 utilized in accordance with the present invention are characterized by the following general formula: It is to be further noted that a mixture of two or more of the above polyalkoxy acetals may be employed with 4 I the organic titanium chelate. 0 T

The foregoing polyalkoxy acetals and numerous species H thereof are prepared in accordance with the methods diswherein R represents either hydrogen or an alkyl radical closed in US. Patents 2,165,962 and 2,487,525. The from 3 to 18 carbon atoms and Y represents the chelating methods of their preparation and the various species dis- 4 radical which is linked to two or more electron donating closed therein, which conform to the foregoing general 5 atoms such as oxygen or hydrogen and characterized by formula are incorporated herein by reference thereto. octylene glycol, triethanolamine or a fatty acid. Such The organic titanium chelates that I employ in comtitanium chelates can also be prepared by reacting glycols bination with the polyalkoxy acetals, are readily obtained of 4 to 8 carbon atoms or amino alcohols such as triin the usual manner by reacting 1 mole of a titanium ethanolamine n ratios f 3 0r 4 mol s per mole ortho ester with 2, 2.2, 3 or 4 moles of either octyl glycol of titanium ortho ester. The titanium chelates based on (2-ethylhexanediol- 1,3), triethanolamine, triethanolamino alcohols can be further reacted with partial or amine-N-salts of fatty acids such as butyric, caproic, complete neutralization with fatty acids of 3 to 18 carcaprylic, capric, undecylic, myristic, palmitic, oleic, linobon atoms. leic, stearic or any of the fatty acids whether saturated As examples of titanium chelates that may be used in or unsaturated so long as they contain from 4 to 18 conjunction with any one of the foregoing polyalkoxy carbon atoms. acetals, the following are illustrative:

V Molar Proportions Organic Titanium Ohelate Ohelating Compound Ti Acid Employttid as Solu- 1. Octylene glycoititanate(OG'I21) 2 moles Oetylene glycol (2-ethyl- 1 40%inbutanol.

hexanediol-l,3). 2. Octylene glycol titanate (OGT2.21) 2% moles1 (lklztylene glycol (2-othyl- 1 38% in butanol.

(X81118 1O 3. Octylene glycol titanate (OGT-3i) 3 moles Octylcne glycol (2-ethy1- 1 40%inbutanol.

hexane diol-i ,3) 4. Octylene glycol titanate (OGT-41) 4 moles Octylene glycol (2-ethyl- 1 Do,

' hexanediol-L3). 5. Triethanolamine titanate (TAT-21)--. 2 moles Triethano1amine. 1 59% in isopropanol. 6. Triethanolamine titanate-N-oleate do 1 Do.

(TAT-O-Qll). 7. Triethanolarnine titanate-N-oleate do 1 2 01610 D0.

(TAT-O-2l2). 8. Triethanoiamine titanate-N-stearate (in 1 1 stearlc Do.

(TAT-S-21l). 9. Triethanolamine titanate-N-linseed do 1 llinseed fatty Do.

acids salt (TAT-B211). acids.

It is to be noted at the outset-that the :use of any one of the foregoingpolyalkoxy .acetalsper se, .including mixturesthereof, does not yield a plasticized phenol-formaldehyde resin having resistance to flaking-or ,cracking. Similarly, the useofthe organic titanium chelateper so does not yield a plasticized film which will exhibit resistance to flaking or cracking. It is only the combination of the two in the aforestated proportions which yields a completely plasticized film having unusual resistance to flaking or cracking, as will be shown hereinafter.

The following examples will-illustrate the various ways in which phenolic-formaldehyde resin may be plasticized to yield a composition which in film formpossesses excellent flexibility and resistanceto flaking or cracking.

All parts given are by weight.

.Example I A film of the above prepared resin solution was cast on a 20 gauge automotive steel panel while employing a gauge with a mil clearance. After /2 hour of air drying, the film was baked for a period of /2 hour at a temperature of 175 C. The cured'film had a thickness of approximately 1 mil. The-film was then evaluated for flexibility while employing a GeneralElectric impact-flexibility tester and was found to give-an impact elongation'of 1%. This low figure is clearly indicative of a very brittle, poorly plasticized film.

The foregoing flexibility tester is commercially available on the open market and entails a solid metal cylin- -der which is-dropped througha guide trap from a. slide of approximately 4 feet. The impactor strikes .thereverse side of the coated testpanel which is supported by a rubber pad so that the circular imprint of the impactor is barely definable in the panel metal. Each end of the impactor is studded with a group of protruding spherical knobs arranged in .a circle. Afteriirnpact, the film is distended according ;to the curvature of the spherical surface forming a knob. The percent elongation ofthe film is a function solely ;of the geometryof the knob itself, and is not dependent upon the rateofdraw, thicknessof the metal panel or-otherdimensions. This apparatus was chosen because it is idealforztesting resin films for their flexibility, either air dried or baked on a metal panel.

Example II To 100-parts of the phenolic-formaldehyde resinsolution as prepared above, were added "25 parts of apolyalkoxy acetal obtained by condensing 1 mole of methanol with 15 moles of vinyl methylether (PMAC-lS). A film was cast on a 20 gauge automotive steel panel while using a gauge with a 5 mil clearance. The coated film was air dried for /2 hour followed by baking at 175 C. for /2 hour. The cured film had a thickness of approximately 1 mil and when evaluated with the General Electric impact elongation tester gave an impact elongation of approximately 1%. This figure indicates a very poorly plasticized film which is unsuitable wherein resistance to flaking or cracking is a prerequisite.

Example III To 100 parts of the phenolic-formaldehyde resin solution prepared as above, were added 15 parts of octylene glycol titanate (commercially available under the brand name OGT2.21 and containing 38% non-volatile in nbutanol). The mixture was stirred and a film cast in the same manner as in Example I. The dried and cured film gave an impact elongation of /2 thus indicating a very poorly plasticized and very brittle film.

From the foregoing examples, it is clearly evident that the use of either a polyalkoxy acetal or an organic titanium chelate by itself as a plasticizer in the phenolicformaldehyde resin gives a very poorly plasticized film having no resistance to flaking or cracking. In other Words, the resulting film is not only poorly plasticized but very brittle. The new and unexpected feature in A large quantity of phenolic-formaldehyde resin solution was prepared in accordance with the foregoing procedure. In addition, a sufiicient quantity of a commercially available phenolic-formaldehyde resin in alcohol, sold under the brand name of Resinox P97% (50% of resin in ethanol), was obtained and utilized for test purposes. Both of the resin solutions were allocated into separate portions each containing 100 parts by weight of the resin based on the non-volatile basis to which was added a mixture of polyalkoxy acetal and the organic titanium chelatein various proportions. The resulting solutions wcre-cast as in Example I and then evaluated on the General "Electric impact elongation tester. The results obtained are tabulated in the following table:

Parts of Phenol- Percent Organic -Polyformal- Parts E.G. Titanium Parts alkoxy Parts dehyde of Impact Ohelate Acetal Resin of P97 Elonga- Illustration tion 5 A 30 100 40 5 F 30 100 40 .10 'H :30 100 60 '15 I 30 100 60 20 '3' 35 100 6O 25 M 30 100 40 30 P 30 100 40 5 Q 30 100 40 10 S 30 100 40 From the foregoing table it becomes clearly manifest ;that a mixture ofiat least 30 parts .by weight of apolyalkoxy acetal and 1 to liparts by weight of the organic titanium chelate per 100 parts of phenolic-formaldehyde resin containing 100% solids yields exceptionally good plasticized films-possessing resistance to .cracking or lflaking. The higheiwpercent of elongation is always indicative of a very well plasticized film.

In order to determine what effect varying amounts of the organic titanium chelate would have on the finished film, 9 separate solutions were prepared in accord ance with the foregoing procedure and the following From the above results, it is clearly evident that increasing the PMAC-IS without the presence of the chelate yields poorly plasticized films. As little as 1 part of the chelate per 33 parts of PMAC-lS gives decidely superior results.

Instead of employing straight alcohol solutions of the phenolic-formaldehyde resins, it is possible to incorporate various fillers and pigments in addition to the polyalkoxy acetal and organic titanium chelates to yield coating compositions having many desirable properties wherein flexibility and resistance to cracking or flaking are necessary prerequisites. The resulting coating compositions are particularly adaptable as bake on enamels. After spray coating application, the enamel is baked for 20-45 minutes at a temperature of 165 180 0., preferably at 175 C.

I claim:

1. A heat curable coating composition comprising 100 parts by weight of a phenol-formaldehyde resin, 30 to 100 parts by weight of a polyalkoxyacetal having the following general formula:

OR r1 H H/ OHs-g:g[C\

L .1. OR

wherein R is an alkyl group of 1 to carbon atoms and m represents an integer of 5 to 25, and 1 to 15 parts by weight of an organic titanium chelate having the following general formula:

(l)Y OH nlo-riora OY OH wherein R represents a member selected from the class consisting of hydrogen and an alkyl group of from 3 to 18 carbon atoms, and Y represents a chelating radical selected from the class consisting of the radical of octylene glycol and CHzCHr- CH2CH2OH);

2. A heat curable coating composition according to claim 1 wherein the chelating radical is (CHzOHzOH):

3. A heat curable coating composition according to claim 2 wherein the triethanolamine chelate radical is neutralized with a fatty acid of from 3 to 18 carbon atoms.

4. A heat curable coating composition according to claim 3 wherein the fatty acid is oleic acid.

5. A heat curable coating composition according to claim 3 wherein the fatty acid is stearic acid.

6. A process of obtaining a heat cured film having flexibility and resistance to flaking and cracking consisting of coating a surface with a composition comprising parts by weight of a phenol-formaldehyde resin, 30 to 100 parts by weight of a polyalkoxy acetal having the following general formula:

7. The process according to claim 6 wherein the chelating radical is 8. The process according to claim 7 wherein the triethanolarnine chelate radical is neutralized with a fatty acid of from 3 to 18 carbon atoms.

9. The process according to claim 8 wherein the fatty acid is oleic acid.

10. The process according to claim 8 wherein the fatty acid is stearic acid.

References Cited in the file of this patent UNITED STATES PATENTS 2,689,858 Boyd Sept. 21, 1954 2,809,184 Langer Oct. 8, 1957 2,871,222 Finestone Jan. 27, 1959 2,901,450 Beacham Aug. 25, 1959 

1. A HEAT CURABLE COATING COMPOSITION COMPRISING 100 PARTS BY WEIGHT OF A PHENOL-FORMALDEHYDE RESIN, 30 TO 100 PARTS BY WEIGHT OF A POLYALKOXYACETAL HAVING THE FOLLOWING GENERAL FORMULA: 